west virginiadepartment of environmental protectionAppendix B.5Carbon AnalysisforPM2.5 and Regional HazePromoting a healthy environment.[This page intentionally left blank.]1Patricia Brewer1,Johann Engelbrecht2, Roger Tanner3,Scott Reynolds4, John Calcagni51VISTAS2Desert Research Institute3Tennessee Valley Authority4South Carolina Department of Health and Environmental Control5Environmental Protection AgencyVISTAS Special Monitoring StudiesCarbon Analyses for PM2.5 and Haze2Presentation Objectives• VISTAS Data Analysis• Special Monitoring Studies• Carbon Studies: C14isotope, Positive MatrixFactorization, and Chemical Mass BalanceAreas with Poorest Visibility are similar to PM2.5 Non-attainment AreasIMPROVE SiteFederalTribalClass I AreasBRET1BRIG1CACR1CADI1CHAS1COHU1DOSO1EVER1GRSM1HEGL1JARI1LIGO1MACA1MING1OKEF1ROMA1SAMA1SHEN1SHRO1SIPS1SWAN1UPBU1Average Extinction for 20% Haziest DaysNew IMPROVE Algorithm2000-2004VISTAS coastalVISTAS inlandnon-VISTAS050100150200250300 SWAN ROMA OKEF EVER CHAS SAMA DOSO SHEN JARI LIGO SHRO GRSM COHU SIPS MACA BRIG BRET MING HEGL UPBU CACR

Extinction (Mm

-1 )Sea SaltCoarseSoilECPOMNH4NO3(NH4)2SO4RayleighSulfate dominates the 20% Haziest Days at VISTAS Class I areasAverage Extinction for 20% Best DaysNew IMPROVE Algorithm2000-20040102030405060 SWAN ROMA OKEF EVER CHAS SAMA DOSO SHEN JARI LIGO SHRO GRSM COHU SIPS MACA BRIG BRET MING HEGL UPBU CACRVISTAS coastalVISTAS inlandnon-VISTAS

Extinction (Mm

-1 )Sea SaltCMSoilECPOMNH4NO3(NH4)2SO4RayleighSulfate also dominates the 20% Clearest Days at VISTAS Class I areasNatural Conditions -- New IMPROVE Algorithm -01020304050 Great Sm o ky Mtns Shenandoah Cape Romain Okefenokee Everglades B re ton *Left = B20%; Center =Average; Right = W20%*Breton based on 2001Q2-2002Q1 & 2002Q4-2003Q3

bext (Mm-1)Sea SaltCMSoilECPOMNH4NO3(NH4)2SO4Rayleigh8Monitoring ObjectivesIdentify sources of organic carbonUse high volume samplers with PM2.5 head andquartz filters at 5 sitesSamples collected April 2004 – May 2005Analyses by Desert Research InstituteSelect 250 samples for carbon analysis (5 sites,50 samples per site including field and lab blanks)Define carbon mass of each sampleCharacterize organic composition (GC/MS)Identify tracers of primary sources of carbon(Chemical Mass Balance and Positive MatrixFactorization)9Monitoring ObjectivesIdentify sources of organic carbonFor same samples, characterize C14isotope and ratio of modern to fossil carbonAnalyses by Woods Hole OceanographicInstitute’s National Oceanographic SciencesAccelerator Mass Spectrometry (NOSAMS)Sources of modern carbon: vegetativeemissions, wood burning, agriculturalburning, cookingSources of fossil carbon: gasoline, diesel,oil10URBANCLASS 1Great Smoky Mtns.Cape RomainRaleighVISTAS Carbon Study SitesShenandoahMammoth Cave11Sources of Organic Carbon:Lessons LearnedModern carbon fraction seldom <0.60,usually >0.70Higher modern carbon at forested sites(GRSM and MACA) than coastal (ROMA) orurban (MILL) sitesHigher total carbon and higher total PM2.5aturban site correspond to lower modern carbonNo clear seasonal trends in modern carbonHypothesize that greater wood burning in wintermonths and greater vegetative emissions inspring/summer12Apr 2004May 200513Fraction Modern Carbon vs. Aerosol CarbonCape Romain, All Seasonsy = 0.045x + 0.556R2= 0.4220.300.400.500.600.700.800.901.000.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0Aerosol C,μg/m3

Fraction Modern Carbon, f m1415Great Smoky Mtns, All Seasonsy = 0.038x + 0.609R2= 0.13620.300.400.500.600.700.800.901.001.100.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00Aerosol Carbon,μg/m3

Fraction Modern Carbon, f mFraction Modern Carbon vs. Aerosol Carbon1617Mammoth Cave, All Seasons0.300.400.500.600.700.800.901.001.100.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0

Fraction Modern Carbon, f mAerosol Carbon,μg/m3Fraction Modern Carbon vs. Aerosol Carbon1819Aerosol Carbon,μg/m3Fraction Modern Carbon vs. Aerosol CarbonMillbrook, All Seasons0.300.400.500.600.700.800.901.001.100.00 2.00 4.00 6.00 8.00 10.00 12.00

Fraction Modern Carbon, f m2021Shenadoah, All Seasonsy = 0.054x + 0.514R2= 0.4340.300.400.500.600.700.800.901.001.100.00 1.00 2.00 3.00 4.00 5.006.00 7.00 8.00 9.00 10.00Aerosol Carbon,μg/m3Fraction Modern Carbon vs. Aerosol Carbon

Fraction Modern Carbon, f m22Monitoring ObjectivesPositive Matrix Factorization applied tocluster organic compounds.Tracers identified forBiogenic EmissionsVegetative BurnGasoline emissionsDiesel emissionsCrude Oil (Commercial Marine, seen at ROMA)Analyses incomplete: tracers still need to berelated back to total carbon to understandrelative importance23Vegetative burnBiogenic EmissionsDiesel CrudeMotor vehicles2425262728Monitoring ObjectivesChemical Mass Balance analysesresults to date from few samples analyzed by MeiZheng, Ga TechChemical markers (profiles) for primarycarbon sources:Wood CombustionGasoline emissionsDiesel emissionsMeat CookingVegetative detritusOther Organic Matter (unidentified primary sourcesplus secondary organics)29GT-CMB Results0.001.002.003.004.005.006.00 ROMA 1-22-04 ROMA 4 - 10-04 GRSM1-22 - 04 GRSM 4 -10 -04 M A C A 1-22 -04 M A C A 4-10 -04 M I LL1-22 - 04 M I LL 4-10-04 SHEN 1-22 - 04 SHEN 4-10-04

μ g/m3DieselGasolineWood CombustionMeat CookingVegetative DetritusOther OM30Carbon Source Attribution:Lessons LearnedCMB Results from samples analyzed byMei Zheng, Ga TechIn April samples from all sites, unidentifiedcomponent is largest fraction (>70%)Likely secondary, likely biogenicWood combustion is largest identifiedcomponent in Jan samples, all sitesGasoline higher in Jan than Apr samples?Diesel at all sites in Apr, not Jan samples?31Carbon Source Attribution:Lessons LearnedCMB analyses together with C14resultsindicate that modern carbon is moreimportant than fossil carbon at Class Iareas and urban area sampled.Little seasonal variability in modern carbonwood burning vs biogenicStill need integration to understand sourcecontributions32Next StepsRelate organic tracers used as PMF factors tolarger population of organic compoundsComplete CMB organic analyses all samplesRelate organic profiles to measured carbonIntegrate results with C14 analysesInterpret source attribution for organic carbonIntegrate results with SOA production inCMAQ/CAMx air quality modelsFinalize project reportsSubmit manucript for publication